Investigation of phenol degradation : True reaction kinetics on fixed film titanium dioxide photocatalyst

This study of photocatalytic oxidation of phenol over titanium dioxide films presents a method for the evaluation of true reaction kinetics. A flat plate reactor was designed for the specific purpose of investigating the influence of various reaction parameters, specifically photocatalytic film thickness, solution flow rate (1–8 l min−1), phenol concentration (20, 40 and 80 ppm), and irradiation intensity (70.6, 57.9, 37.1and 20.4 W m−2), in order to further understand their impact on the reaction kinetics. Special attention was given to the mass transfer phenomena and the influence of film thickness. The kinetics of phenol degradation were investigated with different irradiation levels and initial pollutant concentration. Photocatalytic degradation experiments were performed to evaluate the influence of mass transfer on the reaction and, in addition, the benzoic acid method was applied for the evaluation of mass transfer coefficient. For this study the reactor was modelled as a batch-recycle reactor. A system of equations that accounts for irradiation, mass transfer and reaction rate was developed to describe the photocatalytic process, to fit the experimental data and to obtain kinetic parameters. The rate of phenol photocatalytic oxidation was described by a Langmuir–Hinshelwood type law that included competitive adsorption and degradation of phenol and its by-products. The by-products were modelled through their additive effect on the solution total organic carbon.

Synthesis of novel functional polyolefin containing carboxylic acid via Friedel-Crafts acylation reaction

The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via Friedel-Crafts (F-C) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in order to optimize the acylation process. In the optimum reaction conditions, almost all of the phenyls can be acylated with any anhydride. The microstructure of acylated copolymer was characterized by Fr-IR, H-1 NMR and H-1-H-1 COSY. All the peaks of acylated copolymers can be accurately attributed, which indicates that all the acylation reactions occur only at the para-positions of the substituent of the aromatic rings. The thermal behavior was studied by differential scanning calorimetry (DSC), showing that the melting temperatures (T(m)s) of acylated copolymers with GA firstly decrease slowly and then increase significantly with the increase of the amount of carboxyl acid groups.

Optimisation of Kinetic Parameters for an After-treatment Catalyst

Mathematical modelling has become an essential tool in the design of modern catalytic systems. Emissions legislation is becoming increasingly stringent, and so mathematical models of aftertreatment systems must become more accurate in order to provide confidence that a catalyst will convert pollutants over the required range of conditions. 
Automotive catalytic converter models contain several sub-models that represent processes such as mass and heat transfer, and the rates at which the reactions proceed on the surface of the precious metal. Of these sub-models, the prediction of the surface reaction rates is by far the most challenging due to the complexity of the reaction system and the large number of gas species involved. The reaction rate sub-model uses global reaction kinetics to describe the surface reaction rate of the gas species and is based on the Langmuir Hinshelwood equation further developed by Voltz et al. [1] The reactions can be modelled using the pre-exponential and activation energies of the Arrhenius equations and the inhibition terms. 
The reaction kinetic parameters of aftertreatment models are found from experimental data, where a measured light-off curve is compared against a predicted curve produced by a mathematical model. The kinetic parameters are usually manually tuned to minimize the error between the measured and predicted data. This process is most commonly long, laborious and prone to misinterpretation due to the large number of parameters and the risk of multiple sets of parameters giving acceptable fits. Moreover, the number of coefficients increases greatly with the number of reactions. Therefore, with the growing number of reactions, the task of manually tuning the coefficients is becoming increasingly challenging. 
In the presented work, the authors have developed and implemented a multi-objective genetic algorithm to automatically optimize reaction parameters in AxiSuite®, [2] a commercial aftertreatment model. The genetic algorithm was developed and expanded from the code presented by Michalewicz et al. [3] and was linked to AxiSuite using the Simulink add-on for Matlab. 
The default kinetic values stored within the AxiSuite model were used to generate a series of light-off curves under rich conditions for a number of gas species, including CO, NO, C_{3H8 and C3H6. These light-off curves were used to generate an objective function.} 
This objective function was used to generate a measure of fit for the kinetic parameters. The multi-objective genetic algorithm was subsequently used to search between specified limits to attempt to match the objective function. In total the pre-exponential factors and activation energies of ten reactions were simultaneously optimized. 
The results reported here demonstrate that, given accurate experimental data, the optimization algorithm is successful and robust in defining the correct kinetic parameters of a global kinetic model describing aftertreatment processes.

New catalysts for the water gas shift reaction at middle-temperature

H2 demand is continuously increasing since its many relevant applications, for example, in the ammonia production, refinery processes or fuel cells. The Water Gas Shift (WGS) reaction (CO + H2O = CO2 + H2 DeltaH = -41.1 kJ.mol-1) is a step in the H2 production, reducing significantly the CO content and increasing the H2 one in the gas mixtures obtained from steam reforming. Industrially, the reaction is carried out in two stages with different temperature: the first stage operates at high temperature (350-450 °C) using Fe-based catalysts, while the second one is performed at lower temperature (190-250 °C) over Cu-based catalysts. However, recently, an increasing interest emerges to develop new catalytic formulations, operating in a single-stage at middle temperature (MTS), while maintaining optimum characteristics of activity and stability. These formulations may be obtained by improving activity and selectivity of Fe-based catalysts or increasing thermal stability of Cu-based catalysts. In the present work, Cu-based catalysts (Cu/ZnO/Al2O3) prepared starting from hydrotalcite-type precursors show good homogeneity and very interesting physical properties, which worsen by increasing the Cu content. Among the catalysts with different Cu contents, the catalyst with 20 wt.% of Cu represents the best compromise to obtain high catalytic activity and stability. On these bases, the catalytic performances seem to depend on both metallic Cu surface area and synergetic interactions between Cu and ZnO. The increase of the Al content enhances the homogeneity of the precursors, leading to a higher Cu dispersion and consequent better catalytic performances. The catalyst with 20 wt.% of Cu and a molar ratio M(II)/M(III) of 2 shows a high activity also at 250 °C and a good stability at middle temperature. Thus, it may be considered an optimum catalyst for the WGS reaction at middle temperature (about 300 °C). Finally, by replacing 50 % (as at. ratio) of Zn by Mg (which is not active in the WGS reaction), better physical properties were observed, although associate with poor catalytic performances. This result confirms the important role of ZnO on the catalytic performances, favoring synergetic interactions with metallic Cu.

Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

Alkaline hydrothermal treatment of titanate nanostructures

Since its initial proposal in 1998, alkaline hydrothermal processing has rapidly become an established technology for the production of titanate nanostructures. This simple, highly reproducible process has gained a strong research following since its conception. However, complete understanding and elucidation of nanostructure phase and formation have not yet been achieved. Without fully understanding phase, formation, and other important competing effects of the synthesis parameters on the final structure, the maximum potential of these nanostructures cannot be obtained. Therefore this study examined the influence of synthesis parameters on the formation of titanate nanostructures produced by alkaline hydrothermal treatment. The parameters included alkaline concentration, hydrothermal temperature, the precursor material‘s crystallite size and also the phase of the titanium dioxide precursor (TiO2, or titania). The nanostructure‘s phase and morphology was analysed using X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy (XPS), dynamic light scattering (non-invasive backscattering), nitrogen sorption, and Rietveld analysis were used to determine phase, for particle sizing, surface area determinations, and establishing phase concentrations, respectively. This project rigorously examined the effect of alkaline concentration and hydrothermal temperature on three commercially sourced and two self-prepared TiO2 powders. These precursors consisted of both pure- or mixed-phase anatase and rutile polymorphs, and were selected to cover a range of phase concentrations and crystallite sizes. Typically, these precursors were treated with 5–10 M sodium hydroxide (NaOH) solutions at temperatures between 100–220 °C. Both nanotube and nanoribbon morphologies could be produced depending on the combination of these hydrothermal conditions. Both titania and titanate phases are comprised of TiO6 units which are assembled in different combinations. The arrangement of these atoms affects the binding energy between the Ti–O bonds. Raman spectroscopy and XPS were therefore employed in a preliminary study of phase determination for these materials. The change in binding energy from a titania to a titanate binding energy was investigated in this study, and the transformation of titania precursor into nanotubes and titanate nanoribbons was directly observed by these methods. Evaluation of the Raman and XPS results indicated a strengthening in the binding energies of both the Ti (2p3/2) and O (1s) bands which correlated to an increase in strength and decrease in resolution of the characteristic nanotube doublet observed between 320 and 220 cm.1 in the Raman spectra of these products. The effect of phase and crystallite size on nanotube formation was examined over a series of temperatures (100.200 �‹C in 20 �‹C increments) at a set alkaline concentration (7.5 M NaOH). These parameters were investigated by employing both pure- and mixed- phase precursors of anatase and rutile. This study indicated that both the crystallite size and phase affect nanotube formation, with rutile requiring a greater driving force (essentially �\harsher. hydrothermal conditions) than anatase to form nanotubes, where larger crystallites forms of the precursor also appeared to impede nanotube formation slightly. These parameters were further examined in later studies. The influence of alkaline concentration and hydrothermal temperature were systematically examined for the transformation of Degussa P25 into nanotubes and nanoribbons, and exact conditions for nanostructure synthesis were determined. Correlation of these data sets resulted in the construction of a morphological phase diagram, which is an effective reference for nanostructure formation. This morphological phase diagram effectively provides a .recipe book�e for the formation of titanate nanostructures. Morphological phase diagrams were also constructed for larger, near phase-pure anatase and rutile precursors, to further investigate the influence of hydrothermal reaction parameters on the formation of titanate nanotubes and nanoribbons. The effects of alkaline concentration, hydrothermal temperature, crystallite phase and size are observed when the three morphological phase diagrams are compared. Through the analysis of these results it was determined that alkaline concentration and hydrothermal temperature affect nanotube and nanoribbon formation independently through a complex relationship, where nanotubes are primarily affected by temperature, whilst nanoribbons are strongly influenced by alkaline concentration. Crystallite size and phase also affected the nanostructure formation. Smaller precursor crystallites formed nanostructures at reduced hydrothermal temperature, and rutile displayed a slower rate of precursor consumption compared to anatase, with incomplete conversion observed for most hydrothermal conditions. The incomplete conversion of rutile into nanotubes was examined in detail in the final study. This study selectively examined the kinetics of precursor dissolution in order to understand why rutile incompletely converted. This was achieved by selecting a single hydrothermal condition (9 M NaOH, 160 °C) where nanotubes are known to form from both anatase and rutile, where the synthesis was quenched after 2, 4, 8, 16 and 32 hours. The influence of precursor phase on nanostructure formation was explicitly determined to be due to different dissolution kinetics; where anatase exhibited zero-order dissolution and rutile second-order. This difference in kinetic order cannot be simply explained by the variation in crystallite size, as the inherent surface areas of the two precursors were determined to have first-order relationships with time. Therefore, the crystallite size (and inherent surface area) does not affect the overall kinetic order of dissolution; rather, it determines the rate of reaction. Finally, nanostructure formation was found to be controlled by the availability of dissolved titanium (Ti4+) species in solution, which is mediated by the dissolution kinetics of the precursor.

Intrinsic kinetics of titania photocatalysis : simplified models for their investigation

Even though titanium dioxide photocatalysis has been promoted as a leading green technology for water purification, many issues have hindered its application on a large commercial scale. For the materials scientist the main issues have centred the synthesis of more efficient materials and the investigation of degradation mechanisms; whereas for the engineers the main issues have been the development of appropriate models and the evaluation of intrinsic kinetics parameters that allow the scale up or re-design of efficient large-scale photocatalytic reactors. In order to obtain intrinsic kinetics parameters the reaction must be analysed and modelled considering the influence of the radiation field, pollutant concentrations and fluid dynamics. In this way, the obtained kinetic parameters are independent of the reactor size and configuration and can be subsequently used for scale-up purposes or for the development of entirely new reactor designs. This work investigates the intrinsic kinetics of phenol degradation over titania film due to the practicality of a fixed film configuration over a slurry. A flat plate reactor was designed in order to be able to control reaction parameters that include the UV irradiance, flow rates, pollutant concentration and temperature. Particular attention was paid to the investigation of the radiation field over the reactive surface and to the issue of mass transfer limited reactions. The ability of different emission models to describe the radiation field was investigated and compared to actinometric measurements. The RAD-LSI model was found to give the best predictions over the conditions tested. Mass transfer issues often limit fixed film reactors. The influence of this phenomenon was investigated with specifically planned sets of benzoic acid experiments and with the adoption of the stagnant film model. The phenol mass transfer coefficient in the system was calculated to be km,phenol=8.5815x10-7Re0.65(ms-1). The data obtained from a wide range of experimental conditions, together with an appropriate model of the system, has enabled determination of intrinsic kinetic parameters. The experiments were performed in four different irradiation levels (70.7, 57.9, 37.1 and 20.4 W m-2) and combined with three different initial phenol concentrations (20, 40 and 80 ppm) to give a wide range of final pollutant conversions (from 22% to 85%). The simple model adopted was able to fit the wide range of conditions with only four kinetic parameters; two reaction rate constants (one for phenol and one for the family of intermediates) and their corresponding adsorption constants. The intrinsic kinetic parameters values were defined as kph = 0.5226 mmol m-1 s-1 W-1, kI = 0.120 mmol m-1 s-1 W-1, Kph = 8.5 x 10-4 m3 mmol-1 and KI = 2.2 x 10-3 m3 mmol-1. The flat plate reactor allowed the investigation of the reaction under two different light configurations; liquid and substrate side illumination. The latter of particular interest for real world applications where light absorption due to turbidity and pollutants contained in the water stream to be treated could represent a significant issue. The two light configurations allowed the investigation of the effects of film thickness and the determination of the catalyst optimal thickness. The experimental investigation confirmed the predictions of a porous medium model developed to investigate the influence of diffusion, advection and photocatalytic phenomena inside the porous titania film, with the optimal thickness value individuated at 5 ìm. The model used the intrinsic kinetic parameters obtained from the flat plate reactor to predict the influence of thickness and transport phenomena on the final observed phenol conversion without using any correction factor; the excellent match between predictions and experimental results provided further proof of the quality of the parameters obtained with the proposed method.

A comparative study on pyrolysis for liquid oil from different biomass solid wastes

Locally available different bbiomass solid wastes, pine seed, date seed, plum seed, nutshell, hay of catkin, rice husk, jute stick, saw-dust, wheat straw and linseed residue in the particle form have been pyrolyzed in laboratory scale fixed bed reactor. The products obtained are pyrolysis oil, solid char and gas. The oil and char are collected while the gas is flared into atmosphere. The variation of oil yield for different biomass feedstock with reaction parameters like, reactor bed temperature, feed size and running time is presented in a comparative way in the paper. A maximum liquid yield of 55 wt% of dry feedstock is obtained at an optimum temperature of 500 °C for a feed size of 300-600 μm with a running time of 55 min with nutshell as the feedstock while the minimum liquid yield is found to be 30 wt% of feedstock at an optimum temperature of 400 °C for a feed size of 2.36 mm with a running time of 65 min for linseed residue. A detailed study on the variation of product yields with reaction parameters is presented for the latest investigation with pine seed as the feedstock where a maximum liquid yield of 40 wt% of dry feedstock is obtained at an optimum temperature of 500 °C for a feed size of 2.36-2.76 mm with a running time of 120 min. The characterization of the pyrolysis oil is carried out and a comparison of some selected properties of the oil is presented. From the study it is exhibited that the biomass solid wastes have the potential to be converted into liquid oil as a source of renewable energy with some further upgrading of the products.

Hydrothermal synthesis and characterisation of Cu2ZnSnS4 light absorbers for solar cells

This project has extended the knowledge in the hydrothermal synthesis of copper zinc tin sulphide (CZTS) semiconductor material which is regarded as one of the most promising light absorbing material for PV technologies. The investigation of various reaction parameters on the controlled synthesis of CZTS compound has provided important insight into the formation mechanism as well as the crystal growth behaviour of the material. CZTS nanocrystals with different crystal structure and particle size were synthesised throughout this project. The growth mechanism of CZTS crystals through a high temperature annealing treatment was also explored.

Highly Luminescent Mn-Doped ZnS Nanocrystals: Gram-Scale Synthesis

Following growth doping technique highly luminescent (quantum yield >50%) Mn-doped ZnS nanocrystals are synthesized via colloidal synthetictechnique. The dopant emission has been optimized with varying reaction parameters and found the ratio of Zn and S as well as the percentage of introduced dopant in the reaction mixture are key factors for controlling the intensity. The method is simple, hassle free, and can be scalable to gram level without hindering the quality of nanocrystals. These nanocrystals retain their emission during various ligand exchange processes and aqueous dispersion.

A kinetic study of liquid-phase catalytic oxidation of styrene to benzaldehyde with Wilkinson complex

Liquid-phase homogeneous catalytic oxidation of styrene with Wilkinson complex by molecular oxygen in toluene medium gave selectively benzaldehyde and formaldehyde as the primary products. Higher temperatures and styrene conversions eventually led to acid formation due to co-oxidation of aldehyde.A reaction induction period and an initiation period, typical of free-radical reactions, characterized the oxidation process. The effects of temperature and catalyst and styrene concentrations on the conversion of styrene to benzaldehyde and acid formation have been studied. The optimum reaction parameters have been determined as a styrene-to-solvent mole ratio of 0.5, a catalyst-to-styrene mole ratio of 5.0 X lo4, and a reaction temperature of 75 "C. A reaction scheme based upon free-radical mechanism yielded a pseudo-first-order model which agreed well with the observed kinetic data in the absence of co-oxidation of aldehyde. A second-order model was found to fit the experimental data better in the case of aldehyde conversion to acid.

A simple synthesis and characterization of CuS nanocrystals

Water-soluble CuS nanocrystals and nanorods were prepared by reacting copper acetate with thioacetamide in the presence of different surfactants and capping agents. The size of the nanocrystals varied from 3-20 nm depending on the reaction parameters such as concentration, temperature, solvent and the capping agents. The formation of nanocrystals was studied by using UV-visible absorption spectroscopy.

Study of the growth of capped ZnO nanocrystals: A route to rational synthesis

We report the study of complex and unexpected dependencies of nanocrystal size as well as nanocrystalsize distribution on various reaction parameters in the synthesis of ZnO nanocrystals using poly(vinyl pyrollidone) (PVP) as a capping agent. This method establishes a qualitatively different growth mechanism to the anticipated Ostwald ripening behavior. The study of size-distribution kinetics and an understanding of the observed non-monotonic behaviors provides a route to rational synthesis. We used a simple, but accurate, approach to estimate the size-distribution function of nanocrystals from the UV-absorption spectrum. Our results demonstrate the accuracy and generality of this approach, and we also illustrate its application to various semiconducting nanocrystals, such as ZnO, ZnS, and CdSe, over a wide size range (1.8-5.3 nm).

Pristine nanomaterials: synthesis, stability and applications

Capping-free and linker-free nanostructures/hybrids possess superior properties due to the presence of pristine surfaces and interfaces. In this review, various methods for synthesizing pristine nanomaterials are presented along with the general principles involved in their morphology control. In wet chemical synthesis, the interplay between various reaction parameters results in diverse morphology. The fundamental principles behind the evolution of morphology including nanoporous aggregates of metals and other inorganic materials, 2D nanocrystals of metals is elucidated by capping-free methods in aqueous medium. In addition, strategies leading to the attachment of bare noble metal nanoparticles to functional oxide supports/reduced graphene oxide has been demonstrated which can serve as a simple solution for obtaining thermally stable and efficient supported catalysts with free surfaces. Solution based synthesis of linker-free oxide-semiconductor hybrids and capping-free metal nanowires on substrates are also discussed in this context with ZnO/CdS and ultrathin Au nanowires as examples. A simple and rapid microwave-assisted method is highlighted for obtaining such hybrids which can be employed for high-yield production of similar materials.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.